MPW1K Performs Much Better than B3LYP in DFT Calculations on Reactions that Proceed by Proton-Coupled Electron Transfer (PCET)

摘要

Density functional theory calculations have been performed with the B3LYP and MPW1K functionals on the hydrogen atom abstraction reactions of ethenoxyl with ethenol and of phenoxyl with both phenol and a-naphthol.A comparison with the results of G3 calculations shows that B3LYP seriously underestimates the barrier heights for the reaction of ethenoxyl with ethenol by both proton-coupled electron transfer (PCET)and hydrogen-atom transfer (HAT)mechanisms.The MPW1K functional also underestimates the barrier heights,but by much less than B3LYP.Similarly,a comparison with the results of experiments on the reaction of a phenoxyl radical with a-naphthol indicates that the barrier height for the preferred PCET mechanism is calculated.more accurately by MPW1K than by B3LYP.These findings indicate that the MPW1K functional is much better suited than B3LYP for calculations on hydrogen abstraction reactions by both HAT and PCET mechanisms.